JP7088679B2 - Thermoplastic elastomer composition - Google Patents

Description

The present invention relates to a thermoplastic elastomer composition and a method for producing the same.

Ethylene / α-olefin / non-conjugated polyene copolymers such as ethylene / propylene / diene copolymer (EPDM) are generally excellent in weather resistance, heat resistance, and ozone resistance, and are generally used in automobiles, for example. Is used for vultured rubber products such as glass run channel products, window frame products and hose products.

The dynamically cross-linked thermoplastic elastomer composition (Thermoplastic Vulcanizate; TPV) is generally composed of polypropylene for the sea phase and cross-linked EPDM for the island phase, but since the sea phase is a thermoplastic resin, it is once stretched. The restoration was not enough.

As a composition in which EPDM and an ionomer resin are blended, Patent Document 1 describes the ionomer resin in EPDM-based rubber and dynamically vulcanized the EPDM-based rubber by sulfur vulcanization or resin vulcanization. A rubber composition dispersed in a resin is described. The composition described in Patent Document 1 is used as a rubber roller, and does not disclose a specific composition containing a propylene-based polymer (without a functional group) such as polypropylene. Patent Document 1 discloses a composition in which polypropylene is blended in place of the ionomer resin as Comparative Example 3, but in Comparative Example 3, the fitting workability to the roller shaft was significantly inferior, and the composition was cracked at the time of fitting. There is also a rubber roller, and it is stated that it was not suitable as a paper feed roller because of its extremely small coefficient of friction and large amount of wear.

Patent Document 2 describes synthetic rubber such as EPDM, a thermoplastic resin selected from the group consisting of a maleic anhydride-modified ethylene-based copolymer, an ethylene / unsaturated carboxylic acid copolymer, or an ionomer thereof, a reinforcing agent, and the like. A rubber composition containing a cross-linking agent is described.

However, only sulfur, vulcanizing agents such as sulfur compounds, and organic peroxides are described as cross-linking agents, and no mention is made of phenol-resin-based cross-linking agents. Further, it is a crosslinked rubber composition described in Patent Document 2, and is not a dynamically crosslinked thermoplastic elastomer composition.

Patent Document 3 describes a thermoplastic elastomer composition obtained by cross-linking polypropylene modified with EPDM and maleic anhydride with metal ions.

However, only organic peroxides are described as cross-linking agents, and no mention is made of phenol-resin-based cross-linking agents.

JP-A-11-59950 (Claim 1, paragraph 0040, 0054, Table 2) JP-A-2010-235685 (Claim 1, 3, 4, paragraphs 0040, 0054, Table 2) Japanese Unexamined Patent Publication No. 2011-178827 (Claims 1 and 2, Example 1)

An object of the present invention is to provide a thermoplastic elastomer composition having low permanent elongation and good restoration after stretching.

The gist of the present invention is as follows.
(1) It has at least one functional group selected from ethylene, an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene copolymer (A), and a functional group derived from an unsaturated carboxylic acid or a derivative thereof. Polyolefin resin (B) having a density of 910 to 970 kg / m ³ (may be partially or completely neutralized by metal ions), propylene polymer (C), phenol resin cross-linking agent (D) and A thermoplastic elastomer composition comprising a metal ion source (E).
(2) Ethylene, α-olefin having 3 to 20 carbon atoms, non-conjugated polyene copolymer (A), 10 to 85 parts by mass, and the polyolefin resin (B) (partially neutralized or completely neutralized by metal ions). (May be good) 0.1 to 30 parts by mass, propylene-based polymer (C) 0.1 to 35 parts by mass, phenol resin-based cross-linking agent (D) 1 to 15 parts by mass, metal ion source (E) 0.01 to Including 10 parts by mass (however, the total amount of (A), (B), (C), (D) and (E) is 100 parts by mass), and the total amount of the above (A) to (E). The thermoplastic elastomer composition according to (1) above, which contains 0 to 15 parts by mass of the modified ethylene / α-olefin copolymer (F) having a density of 840 to 900 kg / m ³ with respect to 100 parts by mass.
(3) The composition (X1) containing ethylene, an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene copolymer (A) and a phenol resin-based cross-linking agent (D) is the polyolefin resin (B) and propylene. The thermoplastic elastomer composition according to (1) or (2) above, which is dispersed in the composition (X2) containing the system polymer (C) and the metal ion source (E).
(4) The thermoplastic elastomer composition according to (3) above, wherein the composition (X1) further contains a metal ion source (E).
(5) It has at least one functional group selected from ethylene, an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene copolymer (A), and a functional group derived from an unsaturated carboxylic acid or a derivative thereof. Polyolefin resin (B) having a density of 910 to 970 kg / m ³ (may be partially neutralized or completely neutralized by metal ions), a propylene-based polymer (C), a phenol resin-based cross-linking agent (D), and The method for producing a thermoplastic elastomer composition according to any one of (1) to (4) above, which comprises dynamically cross-linking the composition containing the metal ion source (E).

According to the present invention, it is possible to provide a thermoplastic elastomer composition having low permanent elongation and good restoration after stretching.

Hereinafter, the present invention will be specifically described.

The thermoplastic elastomer composition of the present invention comprises ethylene, an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene copolymer (A), and a polyolefin resin (B) having a functional group such as a carboxylic acid group (with metal ions). It may be partially or completely neutralized), contains a propylene-based polymer (C), a phenolic resin-based cross-linking agent (D), and a metal ion source (E).

[Ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms]
The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention usually contains (a) a unit derived from ethylene and (b) a unit derived from α-olefin. Is in the range of 50/50 to 95/5, preferably 60/40 to 80/20, and more preferably 65/35 to 75/25 [(a) / (b)].

The α-olefin constituting the ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms according to the present invention is usually an α-olefin having 3 to 20 carbon atoms, and specifically. Are propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1- Examples thereof include tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadesen, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like. Of these, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and propylene is particularly preferable. These α-olefins may be used alone or in combination of two or more.

Specific examples of the non-conjugated polyene constituting the ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention include 1,4-hexadiene and 3-methyl-1. , 4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadene, 8-methyl Chain non-conjugated diene such as -4-ethylidene-1,7-nonadien, 4-ethylidene-1,7-undecadien;
Methyltetrahydroinden, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyllidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene , 5-Vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, norbornene and other cyclic non-conjugated diene;
2,3-Diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornene, 4-ethylidene-8-methyl-1,7-nanodiene, etc. Examples thereof include triene, and these non-conjugated polyenes can be used alone or in two or more kinds. Among these non-conjugated polyenes, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) are preferable.

The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention has an iodine value of usually 1 to 50, preferably 5 to 40, which is an index of the amount of the non-conjugated polyene component. , More preferably in the range of 10-30. The total amount of non-conjugated polyene is usually in the range of 2 to 20% by mass in the component (A).

The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention has a limit viscosity [η] measured in decalin at 135 ° C., usually 1 to 10 dl / g, preferably 1 to 10 dl / g. Is in the range of 1.5-8 dl / g.

The ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms according to the present invention is a so-called oil spreading rubber containing a softening agent, preferably a mineral oil-based softening agent, at the time of its production. May be. Examples of the mineral oil-based softener include conventionally known mineral oil-based softeners such as paraffin-based process oil.

The Mooney viscosity [ML _{1 + 4} (100 ° C.)] of the ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms according to the present invention is usually in the range of 10 to 250, preferably 30 to 150. It is in.

The ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms according to the present invention may be used alone or in combination of two or more.

The ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms according to the present invention can be produced by a conventionally known method.

The blending amount of the ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms is based on the total amount of 100 parts by mass of the above (A) to (E) from the viewpoint of heat resistance. It is usually 10 to 85 parts by mass, preferably 20 to 70 parts by mass.

[Polyolefin resin (B) having a functional group such as a carboxylic acid group]
The polyolefin resin (B) according to the present invention has a functional group derived from an unsaturated carboxylic acid or a derivative thereof, and the functional group may be partially or completely neutralized by metal ions. The functional group preferably includes a carboxylic acid group.

From the viewpoint of lightness, the polyolefin resin (B) needs to have a density of 910 to 970 kg / m ³ , preferably 910 to 965 kg / m ³ .

The polyolefin resin (B) according to the present invention preferably includes an ethylene / unsaturated carboxylic acid copolymer.

The ethylene / unsaturated carboxylic acid copolymer is a copolymer of ethylene and an unsaturated carboxylic acid, and has a melting point of usually in the range of 60 to 120 ° C, preferably 70 to 120 ° C.

Examples of the unsaturated carboxylic acid that is copolymerized with ethylene in the ethylene / unsaturated carboxylic acid copolymer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic acid monoesters. More specifically, unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and unsaturated such as monomethyl maleate, monoethyl maleate and monoisobutyl maleate. Examples thereof include dicarboxylic acid monoesters. Among these, acrylic acid or methacrylic acid is preferable, and methacrylic acid is particularly preferable.

The ethylene / unsaturated carboxylic acid copolymer is obtained by copolymerizing not only a binary copolymer of ethylene and an unsaturated carboxylic acid but also another vinyl monomer, for example, a vinyl ester such as vinyl acetate or an unsaturated carboxylic acid ester. It may be a multiple copolymer. Examples of such unsaturated carboxylic acid ester components include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, and maleic acid. Ester and the like can be exemplified. However, those containing a large amount of such other monomers are generally flexible, have a low melting point, and may impair heat resistance. Therefore, when using a multimer copolymer, for example, the content of other monomers is used. It is preferable to use 20% by mass or less, particularly 10% by mass or less. A copolymer serving as such a base polymer can be obtained by radical copolymerization under high temperature and high pressure.

The ethylene / unsaturated carboxylic copolymer is not particularly limited as long as the melting point is within the above range, but the unit derived from the unsaturated carboxylic acid is usually 2 to 20% by mass, preferably 2 to 16% by mass. Is in the range of.

When an ethylene / unsaturated carboxylic acid copolymer containing an unsaturated carboxylic acid ester as a copolymerization component is used as the ethylene / unsaturated carboxylic acid copolymer, the content of the unit derived from ethylene is usually 60 to. 99% by mass, preferably 70 to 94% by mass, the content of the unit derived from the unsaturated carboxylic acid is 4 to 35% by mass, preferably 5 to 30% by mass, the content of the unit derived from the unsaturated carboxylic acid ester. Is 0 to 40% by mass, preferably 0 to 30% by mass. If the content of the unit derived from ethylene is less than the above range, it is difficult to obtain a unit having excellent mechanical strength, which is not preferable. On the other hand, if the content of the unit derived from the unsaturated carboxylic acid is excessively large, it is not preferable because it inhibits the crosslinking reaction. On the contrary, if the content is too small, the effect of improving the rigidity is difficult to obtain. The ethylene / unsaturated carboxylic acid copolymer can be obtained by copolymerizing ethylene, an unsaturated carboxylic acid, or any other vinyl monomer arbitrarily used under high temperature and high pressure.

The molecular weight of the ethylene / unsaturated carboxylic acid copolymer is not particularly limited as long as it can be molded, but usually, the melt flow rate (MFR; ASTM D 1238, 190 ° C., 2.16 kg load) is 0.5 to 5. It is in the range of 1000 g / 10 minutes (dl / g), preferably 1 to 500 g / 10 minutes (dl / g).

As the polyolefin resin (B) according to the present invention, an ionomer resin in which functional groups such as carboxylic acid groups are partially neutralized or completely neutralized by metal ions is preferable, and the ethylene / unsaturated carboxylic co-weight is preferable. Combined ionomers are even more preferred. Examples of the metal ion for neutralization include sodium ion, potassium ion, lithium ion, zinc ion, calcium ion, magnesium ion, aluminum ion and neodymium ion. Neutralization may be done with two or more metal ions. Particularly suitable metal ions from the viewpoint of durability are zinc ions and sodium ions.

Specific examples of ionomer resins include the product names "Himilan 1555", "Himiran 1557", "Himiran 1605", "Himiran 1706", "Himiran 1707", "Himiran 1856", and "Himiran 1855" manufactured by Mitsui DuPont Polychemical. , "HIMIRAN AM7311", "HIMIRAN AM7315", "HIMIRAN AM7317", "HIMIRAN AM7318", "HIMIRAN AM7326", "HIMIRAN AM7329", "HIMIRAN MK7320" and "HIMIRAN MK7329"; , "Salin 6910", "Salin 7930", "Salin 7940", "Salin 8140", "Salin 8150", "Salin 8940", "Salin 8945", "Salin 9120", "Salin 9150", "Salin 9910" , "Sarrin 9945", "Sarrin AD8546", "HPF1000" and "HPF2000"; and ExxonMobil Chemical's trade names "IOTEK7010", "IOTEK7030", "IOTEK7510", "IOTEK7520", "IOTEK8000" and "IOTEK8030". ".

In the thermoplastic elastomer composition of the present invention, by blending the polyolefin resin (B), particularly the ionomer resin, the ionomer resin mixed in the sea phase has a crosslinked structure, so that the sea phase itself is restored after good stretching. Due to the interaction between the ionomer resin and other functional group-containing resins (maleic anhydride-modified EBR) that show properties and are mixed in some island phases, and the ionomer resin in the sea phase, the interfacial adhesive strength is improved and after stretching. It is thought that the resilience will improve.

From the viewpoint of rubber elasticity, the blending amount of the polyolefin resin (B) is usually 0.1 to 40 parts by mass, preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of (A) to (E). It is a mass part.

[Propylene-based polymer (C)]
The propylene-based polymer (C) used in the present invention comprises a high molecular weight solid product obtained by polymerizing propylene alone or propylene and one or more other monoolefins by a high pressure method or a low pressure method.

Suitable raw material olefins other than propylene of the propylene-based polymer (C) are preferably α-olefins having 2 or 4 to 20 carbon atoms, specifically, ethylene, 1-butene, 1-pentene and 1-hexene. , 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like. The polymerization mode may be a random type or a block type as long as a resinous substance is obtained. These propylene-based polymers may be used alone or in combination of two or more.

The propylene-based polymer (C) used in the present invention is preferably a propylene-based polymer having a propylene content of 40 mol% or more, and more preferably a propylene-based polymer having a propylene content of 50 mol% or more.

Among these propylene-based polymers, propylene homopolymers, propylene / ethylene block copolymers, propylene / ethylene random copolymers, propylene / ethylene / butene random copolymers and the like are particularly preferable.

The propylene-based polymer (C) used in the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C., which is usually 0.1 dl / g or more and less than 10 dl / g, preferably 0.5 to 5 dl / g. Is.

The propylene-based polymer (C) used in the present invention has a melting point usually in the range of 80 to 200 ° C, preferably 120 to 170 ° C, and more preferably 145 to 165 ° C.

The propylene-based polymer (C) used in the present invention has an MFR (JIS K6721, 230 ° C., 2.16 kg load) usually in the range of 0.1 to 100 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes. be.

The propylene-based polymer (C) used in the present invention preferably has an isotactic structure as a three-dimensional structure, but has a syndiotactic structure, a mixture of these structures, or a partially atactic structure. Can also be used.

The propylene-based polymer (C) used in the present invention is polymerized by various known polymerization methods.

From the viewpoint of rubber elasticity, the blending amount of the propylene-based polymer (C) is usually 0.1 to 40 parts by mass, preferably 0.1 with respect to 100 parts by mass of the total amount of (A) to (E). It is ~ 35 parts by mass.

[Phenol resin-based cross-linking agent (D)]
In the present invention, the phenol resin-based cross-linking agent (D) is used as the cross-linking agent.
The phenol resin-based cross-linking agent (D) is a resol resin, which is obtained by condensing an alkyl-substituted phenol or an unsubstituted phenol with an aldehyde in an alkaline medium, preferably with formaldehyde, or by condensing bifunctional phenol dialcohols. It is also preferable to be manufactured. The alkyl-substituted phenol is preferably an alkyl group substituted product having 1 to 10 carbon atoms. Further, dimethylolphenols or phenol resins substituted with an alkyl group having 1 to 10 carbon atoms at the p-position are preferable. The phenol resin-based cured resin is typically a heat-crosslinkable resin, and is also referred to as a phenol resin-based cross-linking agent or a phenol resin.

Examples of the phenol resin-based cured resin (phenol resin-based cross-linking agent) include compounds represented by the following general formula (I).

（式中、Ｑは、－ＣＨ_２－及び－ＣＨ_２－Ｏ－ＣＨ_２－から成る群から選ばれる二価の基であり、ｍは０又は１～２０の正の整数であり、Ｒ’は有機基である）。

(In the equation, Q is a divalent group selected from the group consisting of -CH _{2- and -CH 2 -} O-CH _2- , m is 0 or a positive integer from 1 to 20, and R'. Is an organic group).

Preferably, Q is a divalent group-CH ₂ -O-CH _2- , m is 0 or a positive integer from 1 to 10, and R'is an organic group having less than 20 carbon atoms. More preferably, m is 0 or a positive integer from 1 to 5, and R'is an organic group having 4 to 12 carbon atoms. Specific examples thereof include an alkylphenol formaldehyde resin, a methylolated alkylphenol resin, a halogenated alkylphenol resin and the like, preferably a halogenated alkylphenol resin, and more preferably a bromineed terminal hydroxyl group. An example of a phenolic resin-based cured resin having a brominated terminal is shown in the following general formula (II).

（式中、ｎは０～１０の整数、Ｒは炭素数１～１５の飽和炭化水素基である）。

(In the formula, n is an integer of 0 to 10 and R is a saturated hydrocarbon group having 1 to 15 carbon atoms).

Examples of the phenolic cured resin products include Tackylol (registered trademark) 201 (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.) and Tuckylol (registered trademark) 250-I (brominated alkylphenol having a bromization rate of 4%). Formaldehyde resin, Taoka Chemical Industry Co., Ltd.), Tackiroll (registered trademark) 250-III (brominated alkylphenol formaldehyde resin, Taoka Chemical Industry Co., Ltd.), PR-4507 (Gunei Chemical Industry Co., Ltd.) , Vulkarest 510E (Hoechst), Vulkarest 532E (Hoechst), Vulkaresen E (Hoechst), Vulkaresen105E (Hoechst), Vulkaresen130E (Hoechst), Vulkaresen130E (Hoechst) (Manufactured by Rohm & Haas), Sumilite Resin (registered trademark) PR-22193 (manufactured by Sumitomo Durez Co., Ltd.), Symphon-C-100 (manufactured by Anchor Chem.), Symphon-C-1001 (manufactured by Anchor Chem.) , Tamanol (registered trademark) 531 (manufactured by Arakawa Chemical Co., Ltd.), Spectaday SP1059 (manufactured by Spectaday Chem.), Spectaday SP1045 (manufactured by SpectadayChem.), CRR-0803 (manufactured by UCC), Spececty. Examples thereof include SP1055F (Chemistry Chem., Brominated alkylphenol formaldehyde resin), Scienceday SP1056 (Chemistry Chem.), CRM-0803 (Showa Union Synthetic Co., Ltd.), and Vulkadur A (Bayer). Among them, halogenated phenol resin-based cross-linking agents are preferable, and brominated alkylphenol formaldehyde resins such as Tackylol (registered trademark) 250-I, Tuckylol (registered trademark) 250-III, and Schenectady SP1055F can be more preferably used.

Specific examples of cross-linking of thermoplastic vulcanized rubber with phenol resin include US Pat. No. 4,311,628, US Pat. No. 2,972,600 and US Pat. No. 3,287,440. Described, these techniques can also be used in the present invention.

US Pat. No. 4,311,628 discloses a phenolic curative system comprising a phenolic curing resin and a cure activator. The basic components of the system are substituted phenols (eg, halogen-substituted phenols, C1-C _{2 -} alkyl-substituted phenols) or unsubstituted phenols and aldehydes, preferably by condensation with formaldehyde, or bifunctional phenols in alkaline media. It is a phenolic resin-based cross-linking agent produced by condensation of _dialcohols (preferably dimethylolphenols in which the para position is substituted with a C5 _- C10 alkyl group). Halogenated alkyl-substituted phenolic resin-based crosslinkers produced by halogenation of alkyl-substituted phenolic resin-based crosslinkers are particularly suitable. Phenol resin-based cross-linking agents consisting of methylol phenol curable resins, halogen donors and metal compounds are particularly recommended, the details of which are described in US Pat. Nos. 3,287,440 and 3,709,840. Has been done. The non-halogenated phenolic resin-based cross-linking agent is used together with the halogen donor, preferably with a hydrogen halide scavenger. Generally, a halogenated phenolic resin-based cross-linking agent, preferably a brominated phenolic resin-based cross-linking agent containing 2 to 10% by mass of bromine, does not require a halogen donor, but for example, iron oxide, titanium oxide, or oxidation. Used simultaneously with hydrogen halide scavengers such as magnesium, magnesium silicate, silicon dioxide and zinc oxide, preferably metal oxides such as zinc oxide. These hydrogen halide scavengers such as zinc oxide are usually used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the phenol resin-based cross-linking agent. The presence of such a scavenger promotes the cross-linking action of the phenol-based resin-based cross-linking agent, but in the case of rubber that is not easily vulcanized by the phenol-based resin-based cross-linking agent, it is desirable to share the halogen donor and zinc oxide. .. Methods for producing halogenated phenolic curable resins and their use in vulcanizing agents using zinc oxide are described in US Pat. Nos. 2,972,600 and 3,093,613. , The disclosure thereof shall be incorporated herein by reference together with the disclosure of the above-mentioned US Pat. Nos. 3,287,440 and 3,709,840. Examples of suitable halogen donors include stannous chloride, ferric chloride, or halogenated weights such as chlorinated paraffins, chlorinated polyethylene, chlorosulfonated polyethylene and polychlorobutadiene (neoprene rubber). Coalescence is mentioned. As used herein, the term "vulcanization accelerator" means any substance that substantially increases the cross-linking efficiency of phenolic resin-based cross-linking agents, and includes metal oxides and halogen donors, which are these. Is used alone or in combination. For more details on phenolic vulcanizers, see Vulcanization and Vulcanizing Agents (W. Hoffman, Palmerton Publishing Company). Suitable phenolic resin-based crosslinkers and brominated phenolic resin-based crosslinkers are commercially available, for example, such crosslinkers are traded from Schenectady Chemicals, Inc. under the trade names "SP-1045", "CRJ-352". , "SP-1055F" and "SP-1056". Similar operably equivalent phenolic resin-based crosslinkers can also be obtained from other suppliers.

Phenolic resin-based cross-linking agents are suitable vulcanizing agents from the viewpoint of preventing fogging because they generate less decomposition products. Phenolic resin-based crosslinkers are used in sufficient amounts to achieve essentially complete vulcanization of rubber.

From the viewpoint of rubber elasticity, the amount of the phenolic resin-based cross-linking agent (D) is usually 1 to 20 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the total amount of (A) to (E). It is a department.

In the present invention, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrosobenzene, etc. Peroxy cross-linking aids such as diphenylguanidine, trimeryl propane-N, N'-m-phenylenedimaleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimeryl propane. Auxiliary agents such as polyfunctional methacrylate monomers such as trimethacrylate and allyl methacrylate and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

By using the auxiliary agent, a uniform and gentle cross-linking reaction can be expected. Divinylbenzene is preferable as the auxiliary agent. Divinylbenzene is easy to handle, has good compatibility with crystalline polypropylene and ethylene / α-olefin / non-conjugated polyene copolymers contained as main components in the thermoplastic elastomer composition, and is a phenolic resin-based cross-linking agent. Since it has an action of solubilizing and acts as a dispersant for a phenolic resin-based cross-linking agent, a thermoplastic elastomer composition having a uniform cross-linking effect by heat treatment and having a good balance between fluidity and physical properties can be obtained.

The auxiliary agent is usually used in an amount of 2 parts by mass or less, preferably 0.3 to 1 part by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer.

Further, in order to promote the decomposition of the phenol resin-based cross-linking agent, a dispersion accelerator may be used. Examples of the decomposition accelerator include tertiary amines such as triethylamine, tributylamine, and 2,4,6-tri (dimethylamino) phenol; aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead, mercury, etc. Examples thereof include naphthenates of naphthenic acid and various metals (for example, Pb, Co, Mn, Ca, Cu, Ni, Fe, Zn, rare earths).

[Metal ion source (E)]
The metal ion source (E) is a basic metal compound capable of neutralizing an unneutralized functional group such as a carboxylic acid group in the polyolefin resin (B) having a functional group such as a carboxylic acid group.

Examples of the metal ion source (E) include metal hydroxides such as magnesium hydroxide, calcium hydroxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, and copper hydroxide; magnesium oxide, calcium oxide, zinc oxide, and the like. Metal oxides such as copper oxide; metal carbon oxides such as magnesium carbonate, calcium carbonate, sodium carbonate, lithium carbonate, potassium carbonate and the like can be mentioned. These metal ion sources (E) may be used alone or in combination of two or more. Among these, as the metal ion source (E), metal hydroxides such as magnesium hydroxide and calcium hydroxide; and metal oxides such as zinc oxide are preferable.

The blending amount of the metal ion source (E) varies depending on the degree of neutralization of the polyolefin resin (B) to be blended, but from the viewpoint of heat resistance and fluidity, the total amount of the above (A) to (E) is 100 parts by mass. On the other hand, it is usually 0.01 to 15 parts by mass, preferably 0.01 to 10 parts by mass.

[Modified ethylene / α-olefin copolymer (F)]
The thermoplastic elastomer composition of the present invention preferably contains a modified ethylene / α-olefin copolymer (F) from the viewpoint of improving mechanical properties.

The modified ethylene / α-olefin copolymer (F) (hereinafter, may be referred to as “copolymer (F)”) according to the present invention is an unsaturated carboxylic acid for the ethylene / α-olefin copolymer. Alternatively, it is obtained by graft modification with a derivative thereof.

The ethylene / α-olefin copolymer used in the modified ethylene / α-olefin copolymer (F) according to the present invention is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Of these, propylene, 1-butene, 1-hexene and 1-octene are preferable, and 1-butene, 1-hexene and 1-octene are more preferable from the viewpoint of adhesive strength. The ethylene / α-olefin ratio is preferably in the range of 30/70 to 95/5 molar ratio.

Examples of the unsaturated carboxylic acid or its derivative grafted on the ethylene / α-olefin copolymer include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid and acrylic acid. , An unsaturated carboxylic acid such as methacrylic acid, or a derivative thereof, for example, acid anhydrides, imides, amides, esters, etc. of the unsaturated carboxylic acid. Specific examples of the derivative include maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, and glycidylmalate. Among these, unsaturated carboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid, and their acid anhydrides are particularly suitable.

A conventionally known method can be used for graft-copolymerizing a graft monomer selected from such an unsaturated carboxylic acid or a derivative thereof with an ethylene / α-olefin copolymer to produce a modified product. -A melt modification method in which an α-olefin copolymer is melted and a graft monomer is added to carry out a graft copolymerization, or a solution modification method in which the α-olefin copolymer is dissolved in a solvent and a graft monomer is added to carry out a graft copolymerization can be used.

In order to efficiently graft the modification monomer to the ethylene / α-olefin copolymer to obtain the modified ethylene / α-olefin copolymer (F), it is preferable to carry out the reaction in the presence of a radical initiator. In this case, the grafting reaction is usually carried out at a temperature of 60 to 350 ° C. The ratio of the radical initiator used is usually in the range of 0.001 to 2 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin copolymer. Radical initiators include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexine-3, 2,5-dimethyl-2,5. -Organic peroxides such as di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

The amount of the copolymer (F) according to the present invention is preferably modified in the range of 0.01 to 10% by mass, particularly 1 to 5% by mass, as the graft monomer mass (per base polymer). When the amount of graft modification is within the above range, the compatibility with other polymers is good.

The melt flow rate (MFR) of the copolymer (F) according to the present invention is usually 0.1 to 50 g / 10 measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kg according to ASTM D1238. It is preferable that the resin composition is in the range of minutes from the viewpoint of the balance between the processability and the physical properties of the resin composition.

The copolymer (F) according to the present invention preferably has a density of 840 to 900 kg / m ³ from the viewpoint of flexibility.

The blending amount of the copolymer (F) is usually 0 to 20 parts by mass, preferably 0 to 15 parts by mass with respect to 100 parts by mass of the total amount of (A) to (E) from the viewpoint of flexibility and rubber elasticity. It is a mass part.

[Other ingredients]
The composition of the present invention comprises the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms, a polyolefin resin (B), a propylene-based polymer (C), and a phenol-resin-based crosslinker. Components other than the agent (D), the metal ion source (E) and the modified ethylene / α-olefin copolymer (F), for example, conventionally known softeners, inorganic fillers, reinforcing materials, softeners, heat stabilizers ( Additives such as a processing heat stabilizer), an antiaging agent, a weather-resistant stabilizer, an antistatic agent, a crystal nucleating agent, a coloring agent, and a lubricant can be blended within a range that does not impair the object of the present invention.

The softener is a softener usually used for rubber. Specifically, for example, petroleum-based substances such as process oils, lubricating oils, paraffins, liquid paraffins, petroleum asphalt and vaseline; synthetic oils such as low molecular weight ethylene / α-olefin random copolymers; Paraffin oils such as paraffin oil, flaxseed oil, rapeseed oil, soybean oil and coconut oil; waxes such as tall oil, beeswax, carnauba wax and lanolin; Fatroleums such as barium and calcium stearate or metal salts thereof; synthetic polymer substances such as petroleum resin, kumaron inden resin and atactic polypropylene; ester-based plasticizers such as dioctylphthalate, dioctyl adipate and dioctyl sebacate; other microcrystallin wax , Sub (factis), liquid polybutadiene, modified liquid polybutadiene, liquid thiocol and the like. Of these, paraffin-based process oils are particularly preferable.

When a softening agent is added to the composition, it may be added at the time of production of the composition, or ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene copolymer (A), which may be added in advance. Alternatively, a softening agent may be added to a thermoplastic elastomer containing ethylene, an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene copolymer (A), and other components, but the present invention is not limited thereto.

The blending amount of the softening agent is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 40 with respect to 100 parts by mass of ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene copolymer (A). It is up to 150 parts by mass, more preferably 40 to 140 parts by mass. When the softening agent is used in such an amount, the fluidity at the time of producing and molding the composition is excellent, the mechanical properties of the obtained molded product are not easily deteriorated, and the obtained molded product has heat resistance and heat resistance. Has excellent aging properties.

The total amount of the inorganic filler, reinforcing material, heat-resistant stabilizer (processing heat stabilizer), anti-aging agent, weather-resistant stabilizer, antistatic agent, crystal nucleating agent, colorant and lubricant is the above (A) to (E). It is usually 20 parts by mass or less, preferably 19 parts by mass or less, and more preferably 18 parts by mass or less with respect to 100 parts by mass of the total amount.

Specific examples of the inorganic filler include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, silica soil, mica flour, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, and basic magnesium carbonate. , Molybdenum disulfide, graphite, glass fiber, glass bulb, silas balloon, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker and the like.

Examples of the anti-aging agent include aromatic secondary amine-based anti-aging agents such as phenylbutylamine, N, N-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene and tetrakis [methylene (3,5-). Di-t-butyl-4-hydroxy) hydrocinnamate] Phenolic anti-aging agents such as methane; bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide, etc. Thioether-based anti-aging agents; dithiocarbamate-based anti-aging agents such as nickel dibutyldithiocarbamate; 2-mercaptobenzoylimidazole, 2-mercaptobenzoylimidazole zinc salts, dilaurylthiodipropionate, distearylthiodipropionate, etc. There are sulfur-based anti-aging agents.

Examples of the lubricant include higher fatty acid amides, metal shavings, waxes, silicone oils, fluoropolymers and the like. Of these, higher fatty acid amides, silicone oils, and fluoropolymers are preferable.

Examples of the higher fatty acid amide include saturated fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, and behemic acid amide; unsaturated fatty acid amides such as erucic acid amide, oleic acid amide, brush dicic acid amide, and ellagic acid amide. Examples thereof include bis fatty acid amides such as methylene bisstearic acid amide, methylene bisoleic acid amide, ethylene bisstearic acid amide, and ethylene bisoleic acid amide.

Examples of the silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, alkyl silicone oil, fluorosilicone oil, tetramethyltetraphenyltrisiloxane, modified silicone oil and the like.

Examples of the fluoropolymer include polytetrafluoroethylene and vinylidene fluoride copolymer.

[Thermoplastic Elastomer Composition and Its Manufacturing Method]
The thermoplastic elastomer composition constituting the molded product of the present invention is preferably uncrosslinked ethylene, an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene copolymer (A), a polyolefin resin (B), and propylene. A mixture containing a system polymer (C), a phenol resin-based cross-linking agent (D), a metal ion source (E), and an additive to be blended as necessary is dynamically heat-treated and cross-linked (dynamic cross-linking). Obtained by. At least a part of the thermoplastic elastomer composition thus obtained is crosslinked. As described above, only by dynamic cross-linking, a thermoplastic elastomer composition having low permanent elongation and good restoration after stretching can be obtained.

In the present invention, "dynamically heat-treating" means kneading the mixture in a molten state. Further, "dynamic cross-linking" means cross-linking while applying a shearing force to the mixture.

As the kneading device, a conventionally known kneading device such as an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader, a continuous mixer and the like is used. Of these, a non-open type kneading device is preferable, and the kneading is preferably performed in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

The temperature of the heat treatment is usually in the range of 300 ° C. from the melting point of the propylene-based polymer (C), preferably 150 to 280 ° C., and more preferably 170 to 270 ° C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. The shearing force applied is usually 10 to 100,000 sec ^-1 at the maximum shear rate, preferably 100 to 50,000 sec ^-1 , more preferably 1,000 to 10,000 sec ^-1 , and even more preferably 2,000. It is in the range of ~ 7,000 sec ^-1 .

It is presumed that the polyolefin resin (B) such as ionomer resin enters the island phase of the sea-island structure when the compound is kneaded from the beginning, and enters the sea phase when added from the middle of the kneading process. In the general kneading method of the present invention, it is considered that the feed is carried out in the middle of the kneading process and is contained in the sea phase.

The thermoplastic elastomer composition of the present invention obtained by dynamic cross-linking as described above has low permanent elongation and good restoration after stretching, and is therefore suitable for, for example, an automobile sealing material, particularly a glass run channel. Can be used for.

Extrusion molding, blow molding, and injection molding are preferable as the molding method of the molded product using the thermoplastic elastomer composition of the present invention.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the description of the following examples and the like, "parts" means "parts by mass" unless otherwise specified. In the present invention, the parts by weight and the parts by mass are treated synonymously.

[Measurement method and evaluation method]
[Molar quantity and mass of each structural unit of ethylene / α-olefin / non-conjugated polyene copolymer]
The molar quantities and masses of the structural units derived from ethylene, the structural units derived from α-olefins, and the structural units derived from non-conjugated polyenes were determined by intensity measurement using ¹ H-NMR spectrum meter.

[Physical characteristics of thermoplastic elastomer composition]
The method for evaluating the physical properties of the thermoplastic elastomer composition in the following Examples and Comparative Examples is as follows.

[Shore A hardness]
The pellets of the obtained thermoplastic elastomer composition were press-molded at 230 ° C. for 6 minutes using a 100-ton electric heating automatic press (manufactured by Shoji Co., Ltd.), and then cooled and pressed at room temperature for 5 minutes to obtain a press sheet having a thickness of 3 mm. Made. Using the sheet, in accordance with JIS K6253, a type A measuring instrument was used to read the scale immediately after the needle was contacted.

[Tension characteristics]
It was measured according to the method of JIS K6301.
The test piece was used by punching out a No. 3 dumbbell piece from a press sheet having a thickness of 2 mm.
Measurement temperature: 23 ° C
M100: Stress at 100% elongation (MPa)
TB: Tensile breaking strength (MPa)
EB: Tensile breaking point elongation (%)

[Permanent elongation (PS)]
The test piece was used by punching out a No. 3 dumbbell piece from a press sheet having a thickness of 2 mm. This test piece was held at 70 ° C. using a JIS No. 3 dumbbell at an elongation rate of 100% for 22 hours. The length of the test piece 10 minutes after the load was removed was measured, and the permanent elongation (PS) (%) at each heat treatment temperature was calculated from the following formula.

Permanent elongation (PS) (%) = [(t ₁ -t ₀ ) / (t ₂ -t ₀ )] x 100
t ₀ : Length of the test piece before the test t ₁ : Length of the test piece 10 minutes after the load is removed from the test piece t ₂ : Length of the test piece when the test piece is loaded and held

[Compressed permanent strain (CS)]
The pellets of the obtained thermoplastic elastomer composition were press-molded at 230 ° C. for 6 minutes using a 100-ton electric heating automatic press (manufactured by Shoji Co., Ltd.), and then cooled and pressed at room temperature for 5 minutes to obtain a press sheet having a thickness of 2 mm. Made.

A press sheet having a thickness of 2 mm prepared as described above was laminated according to JIS K6250, and a compression set test was performed according to JIS K6262.

The test conditions were 25% compression, compression at 70 ° C for 22 hours, or compression at 125 ° C for 72 hours using laminated sheets with a thickness of 12 mm (4 layers of 3 mm thick pieces) to remove strain (compression). ) It was measured 30 minutes later.

[Repulsive elasticity]
The impact resilience of the composition is the "Lupke-type impact resilience test" in Section 4 of JIS K6255 (1996) "Vulcanized rubber and thermoplastic rubber impact resilience test method" for a composition molded to a thickness of 12 mm and a diameter of 29 mm. It was determined by measuring at 23 ° C. in accordance with the description of.

[Example 1]
[Material used]
(1) Ethylene / α-olefin / non-conjugated polyene copolymer having 3 to 20 carbon atoms (A)
As the ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms, ethylene / propylene / diene copolymer rubber (Mitsui EPT ^TM 3072EPM: manufactured by Mitsui Chemicals Co., Ltd., ethylene content = 64 mass) %, Diene content = 5.4% by mass, Mooney viscosity ML (1 + 4) 125 ° C. = 51, oil spread amount = 40 (PHR)) was used.

(2) Polyolefin resin (B)
As the polyolefin resin (B), an ionomer resin (Himilan ^TM AM7326: manufactured by Mitsui Dupont Polychemical Co., Ltd., MFR (JIS K7210, 190 ° C.), in which the molecules of the ethylene / methacrylic acid copolymer are crosslinked with metal ions (Zn ²⁺ ). 2.16 kg load) 1.1 g / 10 minutes, density (JIS K7112) 950 kg / m ³ , melting point (DSC) 101 ° C.) was used.

(3) Propylene polymer (C)
As the propylene polymer (C), homopolypropylene (Prime Polypro ^TM E111G: manufactured by Prime Polymer Co., Ltd., MFR (JIS K7210, 230 ° C., 2.16 kg load) 0.5 g / 10 minutes, density (JIS K7112) 910 kg / m. ³ ) was used.

(4) Phenol resin-based cross-linking agent (D)
A brominated alkylphenol formaldehyde resin (trade name: SP-1055F, manufactured by Schenectady) was used as the phenol resin-based cross-linking agent.

(5) Metal ion source (E)
Zinc oxide (2 types of zinc oxide, manufactured by HakusuiTech Co., Ltd.) was used as the metal ion source (E).

(6) Modified ethylene / α-olefin copolymer (F)
As the modified ethylene / α-olefin copolymer (F), a maleic anhydride graft-modified ethylene / 1-butene copolymer (Toughmer ^TM MH5020: manufactured by Mitsui Kagaku Co., Ltd., MFR (ASTM D1238, 190 ° C., 2.16 kg load)) 0.6 g / 10 min, MFR (ASTM D1238, 230 ° C., 2.16 kg load) 1.2 g / 10 min, density (ASTM D1505) 866 kg / m ³ ) was used.

(7) Softener As the softener, paraffin-based process oil (Diana Process Oil ^TM PW-100: manufactured by Idemitsu Kosan Co., Ltd.) was used.

Ethylene / propylene / diene copolymer rubber as ethylene / α-olefin / non-conjugated polyene (A) (Mitsui EPT ^TM 3072EPM: manufactured by Mitsui Kagaku Co., Ltd., ethylene content = 64% by mass, diene content = 5.4 mass %, Mooney viscosity ML (1 + 4) 125 ° C. = 51, oil spread = 40 (PHR)) 140 parts by mass, as a propylene-based polymer (C), homopolypropylene (Prime Polypro ^TM E111G: manufactured by Prime Polymer Co., Ltd., MFR ( JIS K7210, 230 ° C, 2.16 kg load) 0.5 g / 10 minutes, density (JIS K7112) 910 kg / m ³ ) 20 parts by mass, as a metal ion source (E), zinc oxide (zinc oxide 2 types, Huxylene) Manufactured by 0.8 parts by mass, as a phenolic resin-based cross-linking agent (D), brominated alkylphenol formaldehyde resin (trade name: SP-1055F, manufactured by Selectday), 8 parts by mass, modified ethylene / α-olefin copolymer (F). ), MFR (ASTM D1238, 190 ° C., 2.16 kg load) 0.6 g / 10 min, MFR (ASTM D1238), ethylene / 1-butene copolymer modified with maleic anhydride graft (Toughmer ^TM MH5020: manufactured by Mitsui Chemicals, Inc.) , 230 ° C, 2.16 kg load) 1.2 g / 10 minutes, density (ASTM D1505) 866 kg / m ³ ) 5 parts by mass, and as a softening agent, paraffin-based process oil (Diana process oil ^TM PW-100: Idemitsu Kosan) 40 parts by mass of extruder (product number KTX-30, manufactured by Kobe Steel Co., Ltd., cylinder temperature: C1: 50 ° C, C2: 90 ° C, C3: 100 ° C, C4: 120 ° C, C5: 180 ° C, C6: 200 ° C., C7 to C14: 200 ° C., die temperature: 200 ° C., screw rotation speed: 500 rpm, extrusion amount: 40 kg / h) were mixed and charged from the C0 portion. In addition, an ionomer resin (Himilan ^TM AM7326: manufactured by Mitsui Dupont Polychemical Co., Ltd., MFR (JIS K7210, 190 ° C.), in which the molecules of the ethylene / methacrylic acid copolymer are crosslinked with metal ions (Zn ²⁺ ) from the C11 portion of the extruder is used. 2.16 kg load) 1.1 g / 10 minutes, density (JIS K7112) 950 kg / m ³ ) 20 parts by mass was added to obtain pellets of the thermoplastic elastomer composition. The formulations and results are shown in Table 1.

[Comparative Examples 1 to 4]
Pellets of the thermoplastic elastomer composition were obtained in the same manner as in Example 1 except that the components and the blending amounts thereof were changed as shown in Table 1. The results are shown in Table 1.

From the results shown in Table 1, it can be seen that the permanent elongation (PS) and the high-temperature compression permanent strain (CS) of the thermoplastic elastomer composition are improved by blending an appropriate amount of the polyolefin resin (B) (ionomer resin). In Comparative Example 4 in which the propylene-based polymer (C) (homopolypropylene) was not blended, TPV formation (resinification) was not possible, and the polymer was solidified in a co-continuous form rather than a sea-island structure.

Claims (4)

Ethylene, α-olefin with 3 to 20 carbon atoms, non-conjugated polyene copolymer (A) having 10 to 85 parts by mass, having at least one functional group selected from functional groups derived from unsaturated carboxylic acid or a derivative thereof. The polyolefin resin (B) having a density of 910 to 970 kg / m ³ (partially neutralized or completely neutralized by metal ions) is 0.1 to 30 parts by mass, and the propylene polymer (C) is 0.1. It contains ~ 35 parts by mass, 1 to 15 parts by mass of the phenol resin-based cross-linking agent (D) and 0.01 to 10 parts by mass of the metal ion source (E) (however, (A), (B), (C), ( The total amount of D) and (E) is 100 parts by mass), and the modified ethylene α- has a density of 840 to 900 kg / m ³ with respect to 100 parts by mass of the total amount of (A) to (E). For 100 parts by mass of ethylene / olefin copolymer (F) (5 × 100) / 148.8 parts to 15 parts by mass and ethylene / α-olefin / non-conjugated polyene copolymer (A) having 3 to 20 carbon atoms. , 80 to 140 parts by mass of softener, inorganic filler, reinforcing material, heat-resistant stabilizer (processing heat stabilizer), anti-aging agent, weather-resistant stabilizer, antistatic agent, crystal nucleating agent, coloring agent and lubricant A thermoplastic elastomer composition having a total amount of 20 parts by mass or less with respect to 100 parts by mass of the total amount of (A) to (E). The composition (X1) containing ethylene, an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene copolymer (A) and a phenol resin-based cross-linking agent (D) is the polyolefin resin (B) and a propylene-based polymer. The thermoplastic elastomer composition according to claim 1, which is dispersed in the composition (X2) containing (C) and the metal ion source (E). The thermoplastic elastomer composition according to claim 2, wherein the composition (X1) further comprises a metal ion source (E). It has at least one functional group selected from ethylene, an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene copolymer (A), an unsaturated carboxylic acid or a functional group derived from the derivative thereof, and has a density of 910. Polyolefin resin (B) at ~ 970 kg / m ³ (partially or completely neutralized by metal ions), propylene polymer (C), phenol resin cross-linking agent (D), metal ion source (E). ), Any one of claims 1 to 3, comprising dynamically cross-linking a composition comprising a modified ethylene / α-olefin copolymer (F) having a density of 840 to 900 kg / m ³ and a softening agent. The method for producing a thermoplastic elastomer composition according to.